Manufacture of useful compounds and products from the seed oil of mallotus philippinensis muell. arg.



indies Patented Aug. 3, 1954 MANUFACTURE OF USEFUL COMPOUNDS AND- PRODUCTS 'FROMTHE. SEED OIL .OF'

.( KAM-ALA) MALLDTUS PH'ILIPPINENSIS MUELL. ARG.

Joti'. S'arup Aggarwal, Poona, Vi'shwa Nath' Sharma; Lucknow,- and Sush-il Chandra Gupta, Roona, India, assignors to The Council of Scientific and Industrial Research, New Delhi, India Nomawing. Application February 7, 1952,

" Serial No; 270,526

.Claimsxpriority, application Great Britain 7 September 4, 1951 7 Claims. 1 Z

invention relates-to. the utilization .of the seed oilofiMdllotus philippinensis -Muelll. Arg.

(Kamalal.

Messrs. J. S. Agearwal, s. s. Bhatnagar, Prakash' Narain and Karimullah .(Jour. Sci.Ind. Res, India, ,l948;V,lIB.l136) carried out a preliminary investigation for the separationof the fatty acids present in the seed oil ofMallogtus philippinensis M11611; Arg. (Kamala) as'a result of which they reported 'theisolation of an acid melting at" sis MuelLArg- (Kamala) and for-producing from. thesa-idqseed oil compounds: which could beused:

as; starting. materials. for the .1 manufacture of products of industrial. importance such as odoriferous polymembered carbon rings,1.high .polymeriosubstances aspoly and superpoly esters and nolyamides; detergents; wetting agents, disinfectantsand like materials.

Our; invention includes within... its :scope. the.= production of :long straight chainialiphatic' com pounds cont/aiming. eighteen; carbon atoms: with a primary alcoholic group and a carboxyl group or two carboxyl groups'in'theterminal positions, from-the seed; oil. of Mallotus. philippinensz's Muell. Arg. (Kamala) or the fatty acids derived therefrom.

More particularly, the invention includes the isolation of a. new: acid: which we. designate anKamlolenic acid from .the fatty .-.acidsi of the seed. Oil of Ma low-.5 Philippinensis Muell.. Arg. (Kamala). The process for the isolation of the newacid consists broadly: in theseparation of the.

newv acid from the total. fatty acidsobtained after hydrolysis of the above. 011, .bymeans of organic solvents, in which thesaidacid is very' slightly soluble. Thus thetotal fatty:acidsobtained'after;

saponification ,of the seedoil contain the un-.

saturated acid. a-Kamlolenic. acid, melting. at.

78-79" C. and. conforming to the molecular for mulaCmHsoQa, which can be isolated. to; theextent of.40 to 60. per-cent. of the weightof the oil by the addition of a suitable organic solvent or solvents as describedbelow to the mixtureot:

the total fatty-acids.

a-Kamlolenic acid is. cqnvertedzinto.the'isomerice-form,- melting at 90-.-9 1?. 'C., onexposure either as-such. or inrthe presence. ofran organic-solvent to u-ltraviolet light with. or without the-help of catalysts. fi-isomerby the irradiation ofthe acid by ultraviolet light, as such or in the presence of organic solvents, cooling and subsequent separation. andv purification.

fi-Kamlolenic acid may alsobe obtained fromv the total fatty acid of the seed oil 'of'Mall'otus.

philippinensis Muell.Arg...(Kama1a) by taking the total fatty acids in organic solvents and irra.-. diation in ultraviolet light with or without the presence of catalysts, coolin v and subsequent separation and purification;

Thus ,B-Kamlolenic acid can be obtained. either.

from oc-KELlIllOlGllic acid or the totalfatty acids. derived fromthe seed oil of Mallotus philippinen- V.

sis Muell. Arg. (Kamala).

Both the aand the e-Kamlolenic acids have been found by us to contain a long, straight chain... of-eighteen'carbon atoms with' three double bonds and a primary alcoholic and a carboxyl' group,

in the terminal positions. Out of theethree double bonds,-'two'are in the conjugated positions while the third one is present between the ninth l and the tenth carbon atoms in both the isomers- On the basis of our experimental findings which.- will be published shortly, we have assigned one' or the other of the following two structures to the isomeric acids:

0H-O'HrO.HzCH2CH=OH-CH=GH CHTCH=CH 0159100011 Both the. zxandthe e-Kamlolenic acids on.

reductionunder varying. conditions give rise to di'-, tetra-,' or the hexahydro- Kamlolenic acids,

the 'finally reduced hexahydro derivative being,

identical with w-hYdIOXY stearic acid, melting at 99-100 0. The partially reduced acidsor the hexahydroKamlolenic acid. (w-hydroxy stearicv acid) canalso be obtained by thehydrogenationof the oil followed by saponification and separation of the component acids through the use of single or" mixed solvents. Kamlolenic acid (o-hydroxy stearic acid) on oxidation with potassium permanganate in ace-.

tone solution we have further obtained hexadece. amethylene 1:16-dicarboxylic. acid melting. at

-126 C'. which therefore, must be regarded as..-

having'been obtained from a hitherto. unknown source.

aand the e-Kamlolenic acids, their di-, tetra.-, or the hexa-hydro-derivatives or hexadecamethe ylene lzlfi-dicarboxylic' acid, obtained. in the.

above mentioned manner; form starting materials for the 'manufacture of products of indusa-Kamlolenic acid converted .to. its

From the .hexahydrm gents, wetting agents, bactericides and the like materials.

The following examples illustrate the nature of the invention and are given in order to give a clear idea of the processes described herein but do not in any way limit the scope of the invention. a

EXAMPLE I Isolation of aKamZoZenic acid from Kamaia seed oil 100 gms. of the oil from the seeds of Mallotus philippinensis Muell. Arg. (Kamala) was refluxed with 500 c. c. of alcoholic potash containing 20-22 gms. of caustic potash for one hour. Most of the alcohol was distilled off and the resultant potassium soap was dissolved in about one liter of water. The unsaponifiable matter was removed by shaking the solution with ether. The free acids were then liberated from the soapsolution by hydrolysis in an atmosphere of carbon dioxide or nitrogen by the addition of dilute sulphuric acid. The liberated fatty acids were taken up in ether, the ether solution was washed with cold water, dried over anhydrous sodium sulphate and freed of the solvent, the last traces being removed under reduced pressure. To these acids about 500 c. c. of petroleum ether was added and the whole mixture was thoroughly shaken. The insoluble precipitate was collected and crystallised from benzene in pale white needles, M. P. 78-79 C.; neutralization value, 190.9; equivalent weight 293.3; iodine value (Wijs) 186.2; iodine value (Woburn B) 226.8; diene value (Ellis and Jones method) 120.6; found C, 72.8; H, 10.25; CmHsoOs requires C, 73.47; H, 10.2%; soluble in alcohol, chloroform and carbon tetrachloride. The acid is very unstable and polymerises into rubber mass after two days at 30-40 C. It can, however, be kept for a long time under petrol ether at low temperature.

EXAMPLE II Formation of B-Kamlolenic acid 100 gms. of aKamlolenic acid prepared from Kamala oil by the process described in Example I was suspended in petrol ether (GO-80 C.) in which a crystal of iodine was dissolved. The mixture was irradiated in ultraviolet light in a quartz flask for 3 hours and then cooled in ice, filtered and crystallised from benzene when white needles melting at 90-91" C. were obtained. Yield almost quantitative; neutralization value, 191.1; equivalent weight 293; iodine value (Wijs) 195.4; iodine value (Woburn B) 248.3; diene value (Ellis and Jones method) 120.6; found C, 72.9; H, 10.15; Ciel-T3003 requires C, 73.47; H, 10.2 soluble in alcohol, chloroform and carbon tetrachloride. The alkali soap of this acid is less soluble in water than that of a-Kamlolenic acid. The acid is very unstable and polymerises into a rubbery mass after two days at 30-40 C. It can, however, be kept for a long time under petrol ether at a low temperature.

The same acid (fi-Kamlolenic acid) was isolated directly from the total Kamala oil fatty acids obtained as in Example I by dissolving them (50 gms.) in low boiling petroleum ether (500 c. c.) in a quartz flask and irradiating in ultraviolet light in the presence of traces of iodine. After three hours'the solution was cooled and then precipitated and separated. The filtrate was concentrated to some extent and again irradiated and cooled. After repeating this treatment thrice, the acid was almost completely removed. (Yield about 25 gms.) It was crystallized from benzene in while needles, meltin at 91 0., mixed melting point with B-Kamlolenic acid obtained as above, 90-91 C.

EXAMPLE 111 Production of hemwhydro Kamlolem'c acid (a:- hydrozcy stearic acid) 3 gms. of ec-Kamlolenic acid was dissolved in c. c. of alcohol and hydrogenated in presence of platinum catalyst (0.1 gm.) at ordinary temperature till no more hydrogen could be absorbed. The platinum was separated by filtration. Alcohol was distilled off and pale white substance was crystallized, first from benzene and then from ethyl acetate to white needles M. P. 98-99 C. equivalent weight 304.5; mol. weight 324; found C, 71.41; H, 11.69; CmHseOs requires C, 72.0; H, 12; acetyl value, 164. When p-Kamlolenic acid was hydrogenated under similar conditions the corresponding hexa-hydro acid was again obtained which was identical with the product derived from u-Kamlolenic acid as above.

EXAMPLE IV Production of hemd-hydro-Kamloienic acid (whydromy stearic acid) directly from Kamald seed oil 10 gms. of Kamala seed oil was dissolved in 200 c. c. of alcohol and was hydrogenated in presence of 0.3 gm. platinum catalyst at ordinary temperature till no more hydrogen was absorbed. The spent catalyst was filtered off and alcohol was removed by distillation. The residue of hydrogenated fat was converted to free fatty acids by the method given in Example I. The acids so obtained were shaken with petrol ether. The insoluble portion was separated, washed with petrol ether and crystallized from ethyl acetate; M. P. 919-100 0., mixed M. P. with hexa-hydro Kamlolenic acid, obtained in Example III, 99 C.

EXAMPLE V Heradecdmethylene 1:16-dicarboxylic acid from aor p-Kamlolem'c acid Hexa-hydro Kamlolenic acid (w-hydroxy stearic acid) was obtained from aor fi-Kamlolenic acid as in Example III or IV. 5 gms. of this hydrogenated acid was dissolved in 100 c. c. of pure acetone and powdered potassium permanganate was added in small amounts keeping the solution boiling on the water bath. The violet colour persisted even on boiling for two hours when 5 gms. of potassium permanganate had been added. After distilling off the acetone water was added and enough dilute sulphuric acid to make it acidic. Sulphur dioxide was passed till the precipitated manganese dioxide was dissolved. The solution was cooled, when the white crystalline substance separated. It was filtered, washed with cold water and dried over porous plate. After crystallization from acetone three times, fiufiy white needles of hexadecamethylene lzlfi-dicarboxylic acid melting at -126 C. were obtained. Equivalent weight, 157.6; the acid is sparingly soluble in alcohol,

acetone and ether. The alkali salt was sparingly 5 soluble in Water. Dimethyl ester M. P. 62.:5- 63.1-5 C.

We claim:

1. In the process of separating alpha-Kamlolenic acid from the total fatty acids contained in the seed oil of Mallotus philippinensis Muell. Arg. (Kamala), the steps which comprise treating the said total fatty acids with petroleum ether to remove impurities, separating the resulting insoluble precipitate of alpha-Kamlolenic acid, dissolving the latter in an organic solvent and crystallizing it from the solution.

2. The process of claim 1 followed by irradiating the separated alpha-Kamlolenic acid with ultraviolet light to produce beta-Kamlolenic acid.

3. The process of claim 2 wherein the alpha- Kamlolenic acid is irradiated in the presence of an organic solvent for the acid and traces of iodine.

4 The process of claim 1 followed by hydrogenating the separated alpha-Kamlolenic acid to produce omega-hydroxy-stearic acid.

5. The process of claim 4 wherein the alpha- Kamlolenic acid is hydrogenated in the presence of a hydrogenating catalyst and of a solvent for the alpha-Kamlolenic acid.

6. The process which comprises dissolving Kamala seed oil in an organic solvent, hydrogenating the resulting solution until no more hydrogen is absorbed, removing the organic solvent from the hydrogenated fat, separating fatty acids from the hydrogenated fat, treating the fatty acids with petroleum ether to remove impurities, and recovering the insoluble precipitate of omega-hydroxy stearic acid.

7. In the manufacture of alpha-Kamlolenic acid, the process which comprises treating Kamala seed oil with a solution of caustic alkali in alcohol to sapenify it, treating the resulting alkali soap with an acid to liberate the fatty acids, treating with petroleum ether to remove impurities, recovering the resulting insoluble precipitate of alpha-Kamlolenic acid and crystallizing the latter from benzene.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,159,700 Hennig May 23, 1939 2,591,110 Weisler Apr. 1, 1952 OTHER REFERENCES Hilditch et al., Jour. Soc. Chem. Industry, July 1939, pages 233-244.

Aggrawal et al., Chemical Examination of the Seeds of Mallotus Philippinensis, 43 C. A. 4027 (1949). 

6. THE PROCESS WHICH COMPRISES DISSOLVING KAMALA SEED OIL IN AN ORGANIC SOLVENT, HYDROGENATING THE RESULTING SOLUTION UNTIL NO MORE HYDROGEN IS ABSORBED, REMOVING THE ORGANIC SOLVENT FROM THE HYDROGENATED FAT, SEPARATING FATTY ACIDS FROM THE HYDROGENATED FAT, TREATING THE FATTY ACIDS WITH PETROLEUM ETHER TO REMOVE IMPURITIES, AND RECOVERING THE INSOLUBLE PRECIPITATE OF OMEGA-HYDROXY STEARIC ACID.
 7. IN THE MANUFACTURE OF ALPHA-KAMLOLENIC ACID, THE PROCESS WHICH COMPRISES TREATING KAMALA SEED OIL WITH A SOLUTION OF CAUSTIC ALKALI IN ALCOHOL TO SAPONIFY IT, TREATING THE RESULTING ALKALI SOAP WITH AN ACID TO LIBERATE THE FATTY ACIDS, TREATING WITH PETROLEUM ETHER TO REMOVE IMPURITIES, RECOVERING THE RESULTING INSOLUBLE PRECIPITATE OF ALPHA-KAMLOLENIC ACID AND CRYSTALLIZING THE LATTER FROM BENZENE. 